Treatment of textiles



proof.

in as aluminum acetate, aluminum formate, alum, would become altogether discharged at the s0 10.

' According to another process they have been In addition, most of these treating processes 15 v usually been negatively charged when prepared An object of the p t invention s to P d 20,

the aluminum salt was combined with the col- ,Another object is to p v 8 le npr 251 or about 10% to 30% of oily, waxy or fatty maother textile materials of better quality. so.

may be utilized as the concentrated emulsion. :tionand without the need o pec a p ecau n 6- 40 mospheric electrical charges, changes would take tor-insoluble materials? tainable with the usual bath or impregnating s0- colloidal dispersions in which the water-insoluble be'altogether devoid of water-repelling proper- In preparing these concentrated dispersions,

Theory of Emulsions and Emulsification, p. 104 leum jelly, mineral-oil, stearic acid, neats footloi Patented on. 1, 1935 v 2,015,865

UNITED STATES-PATENT 0-FFlCE"-=- f* I raaammorraxms I necessitate, serene-.1: Produktc, Zurich, Qwiherland, a corporation of Switzerland. I I

No Drawing. i 3,1933, serial No. 859,506

The present invention relates to the treatment and et sequitur), but hitherto no means have of textiles andparticulariy relates to processes been available for overcoming those disturbance: and emu], ms for improving the properties of in emulsions for the treatment of textiles. textiles and especially for rendering them water In preparing emulsions for the single bath process above described, considerable difficulty -5 Textiles and textile fabrics have been water was often experienced in adding the aluminum prooied by treatment with emulsions of fats, oils, salt to the dilute emulsion. The addition of the waxes, paraffin, and other water -insoluble maaluminum salt decreases the negative charge of terials, and with solutions of aluminum salts, such he emulsified p rti l an f q en ly they and other similar salts. According to one proccalled iso-electrical point. At the iso-electrical es the fabrics have been treated successively first point ul tion w uld f n mi n wh n with the emulsion or colloidal solution and sec- .such coagulation ensued, the treating solution ondly with the solution of the aluminum salt. would be of no value.

treated with both the dispersed water-insoluble above described could not be satisfact ily all material and aluminum salt in a single bath or plied to woolen goods, and in case woolen goods 4 were employed, unsatisfactory impresation usu-v These emulsions or colloidal dispersions ha've y resultedwith an emulsifying agent and with a protective an impre nating D s textiles in w i the colloid, such as glue. When a treating solution ac i n will be reliable at all times. and will not or dispersion was prepared containing both the par i ly a f d y xt na l ri l D aluminum salt and the water proofing material, t nt al 1 m p i h loidal dispersion in relatively dilute form. n'ating' process in which the impregnating solu- These baths of the prior art are prepared by tions are of such composition and character that first diluting a concentrated emulsion which conmore Satisfactory d uniform p tion will tains at least 15% of non-aqueous constituents be obtained to produce impregnated fabrics and terials with 20, 50, or more parts of water, and Another object is to provide a process of treatthen after such dilution, adding a corresponding ins x l s in wh h colloidal dispersions Wflquantity of an aluminum salt solution. For ex-. tier-insoluble materials maybe prepared, includample, the.same quantity of aluminum acetate in: aluminum salts, without danger of coagula This mixture is then ready for use. in diluting the colloidal dispersion or emulsion These impregnating solutions, as above dewith water.

scribed, are not altogether satisfactory, because 1 Anothercbiect is -to'- provide a process. of im-' of their instability. Under the influence of at: pregnating woolen goods with emulsions of wo place in the emulsion which would considerably Other objects are in part obvious and inpart reduce and even completely arrest the impregnapointed out hereinafter.

tion action. For example, shortly before a thun- In acc p the forego n Objects it as der storm no impregnating efiect would be obbeen found desirable to treat textile fabrics with lutions, whereas after such electrical disturbance fatty, waxy. or oily materials and a solublealumb the impregnating action would again take place num salt have been combined-in the concentrated in the desired manner. The fabrics or materials dispersions before such dispersion has been ditreated during such electrical disturbances would luted to form a suitable treating bath or solution;

ties, or on the other hand would possess them to preferably mineral, vegetable and/or animal fats, only a slight degree. That external electrical oils and/or waxes are put 'intocollcidal disperpotential discharges have a substantial effect sion in water, preferably by a mechanical homo--- upon emulsions is well known (see Clayton, The genizing process. Parafiln, petrolatum or petro= of emulsion in amount ranging from 10 to I oil, benzol, bees wax, paraffin oil, asphalt, caoutchouc, fatty acids, halogen derivatives of hydrocarbon, hydrogenated aromatic compounds and bituminous substances may all be employed singly or in combination. Preferably in making up the emulsion the water-insoluble material or materials are used in such proportion as to make up at'least 8 to 10% of the concentrated emulsion.

These concentrated emulsions or colloidal dispersions generally should contain more than 15% of non-aqueous material.

In preparing these'emulsions, protective colloids, such as glue, albumin, gelatine, casein, starch, gums, dimethyl-cellulose, protalbic acid, carbohydrates. sulphite waste liquors and other similar materials may be employed, preferably 100% in par-ts by weight of the water insoluble material.

In preparing certain emulsions according to the present invention it is sometimes desirable to use emulsifying agents, such as soap, sulphonated oils, aromatic sulphonic acids. and so forth, but frequently the addition or such emulsifying agents is not necessary. r

A particular feature of the present invention resides in the incorporation in' these concentrated emulsions of soluble aluminum salts,- such as aluminum acetate, aluminum formate, aluminum sulphate, alum, and so forth. It is, however, contemplated th t the aluminum salt may in part or whole be replacedby other polyvalent salts, such as copper. sulphate, lead acetate, ferric sulphate, thorium nitrate, as well as acids, such as sulphuric acid, hydrochloric acid, acetic acid and formic acid. These aluminum salts, or other polyvalent salts, or acids are preferably used in a quantity varying between 5 to 100% or more of the water insoluble colloidal material.

In preparing these emulsions or colloidal dis- -persions the aluminum salt may be conveniently added to the aqueous glue or protective colloid solution and the paraffin or other water-insoluble substance may be emulsified into or homogenized with the aluminum salt and glue solution. Parafphonic acids, and so forth. To this concentrated 7 emulsion after it has been homogenized, maythen be added aluminum salts and/or other charge rewhich usually become solid or semi-solid upon cooling, are then diluted with 20 to 50 or more parts by weight of water for each part by weight to obtain the desired treating solution or bath which is contacted with the .fabric or othertextile material.

Colloidal solutions or dispersions prepared in this manner appear to be positively charged instead of negatively charged, and they are extremely stable and will give veryimp'regnating effects substantially regardless of electrical conditions. The concentrated emulsions may be diluted merely by the addition of water without special precaution to prevent c0- agulation and the impregnating process proceeds with great expedition and with more efiicient utilization of the water-insoluble impregnating materials which aremost effectively removed from a treating bath. by the textile material or fabric. The treating solutions of the present invention are particularly are very satisfactorily treated therewith.

atmospheric Although the present invention is particularly applicable to the impregnation and especially the water proofing of woolenv materials, it is also broadly applicable to the treatment of other textile materials, to the treatment of artificial or 5 natural silk, to the treatment of paper and paper pulp, to the treatment of furs, leather and skins, and other materials.

The following are a few illustrative examples of difierent embodiments of the present invention,-to which the invention is not to be restricted.

Example 1.-300 parts of paraffin are homo genized with a solution of 100 parts of glue and 50 parts of an emulsifying agent as a. sulphonated oil or the sodium salt of an aromatic sulphonated acid in 500 parts of water. 100 parts of the emulsion so prepared are then heated to 910 to 50 0. and 15 parts of pulverized solid aluminum acetate are stirred into the emulsion. The product obtained forms a stable plastic mass when 20 cold.

This emulsion may also be prepared by first addingthe aluminum acetate to an aqueous glue solution and then emulsifying the parafiin in this aqueous glue solution in which case the emulsify- 25 ing agent may be omitted. 5 kilograms of the final emulsion may then be dissolved in from 3 to 4 times this quantity of warm water and added to a bath for treating textiles, the total volume of the bath being preferably 100'liters. 30 A woolen material may then either be milled in this liquor, or be treated on a broad washing machine, or simply be immersed in the liquor until uniformly impregnated. After centrifuging or wringing out of the woolen goods, they are 35 dried as usual. The dried materials will possess very high water-repellant properties without their feel, color or permeability being at all modifled.

Example 2.--To a solution of partsof gela- 401 tine in 700 parts of water areadded parts of solid aluminum acetate. The mixture is warmed at 60 until a uniform solution is obtained. This solution is used to emulsify a melted mixture of 125 parts of petroleum jelly and 125 parts of 45- uct. After this treatment the paper material will 50' possess excellent water-repelling properties which can not be disturbed by the addition of subversing materials. These concentrated emulsions stances increasing the stifiness of the paper, such as glue or rosin soaps, and so forth.

EzampZe 3.-In 1,000 parts of water, of gelatine are dissolved. To this warm solution 50 parts of aluminum sulphate are added and the solution is then stirred until it becomes homogeneous. In this res ltant solution then 40 parts of mineral oil and parts of stearic acid are 60 emulsified. A similar product is obtained as in Examples 1 and 2. I e

A bath containing 3 to 5% of this emulsified product may be utilized for the water proofing of chamois leather. 65

Example 4.-- bath containing 1 to 1 of the concentrated emulsions prepared according to Examples 1, 2 and 3, may be utilized to give water-repellent properties to artificial silk. The silk so treated will be completely resistant to the 70 influence of atmospheric moisture.

The following area series of examples of the composition of other emulsions which may be conand utilized as above described these emulsions being preferably pre- 75 80 parts 55-.

The present application is pared by mechanical homogenization 'of'the insoluble material with an aqueous solution of glue or gelatine and of the soluble polyvalent salt or acid.

Example 5.-20.5 kilograms of para filn, 2.5 kilograms of glue from hides, 6 kilograms oi alumi-.' num sulphate and 71 liters of water. 4

Example 6.-20.5 kilograms of neats foot oil, 5.6 kilograms of bone glue, 17.3 kilograms of aluminum sulphate and 56.5 liters of water.

Example 7.24.4 kilograms of paraflin, 6.7 kilograms of glue, 1 liter of 50% acetic acid,and 67.9 liters of water.

Example 8.-17 kilograms of paraffin, 5 kilograms of glue, 5 liters of 30% acetic acid, and 34 liters of aluminum acetate solution (25 grams ALaOa per liter) and36 liters of water.

Example 9.-19 kilograms of parafiin, 5.3 kilograms of glue, 23 kilograms of crystallized copper sulphate and 52.7 liters of water.

Example 10.--17.3 kilograms of paraflin, 4.9 kilograms of glue, 27.8 kilograms of sugar of lead, and 50 liters of water.

Example 11.12.4 kilograms of paraflln, 6.2

phate, and 78.2 liters of water.

. Example 12.23 kilograms of paraflin oil, 4.1 kilograms of glue, 41 kilograms of dimethylcellulose, 3.6 kilograms of thorium nitrate (crystallized), and 65.2 liters of .water.

All of the emulsions according to the above description have positively charged dispersed phases and when they are subjected to electrical currents the dispersed particles will tend to move to the cathode. These emulsions are all perfectly stable in the concentrated form in which they are prepared. The non-aqueous content of these concentrated emulsions average usually substantially above 15%.

These emulsions will remain unchanged even after they have been kept for days at temperatures of zero to F. At high temperatures of about 100 F. for example, these emulsions will remain completely stable, as contrasted to the usual negatively charged emulsions, which contain no aluminum salts or similar electrolytes. These latter emulsions will be destroyed if they are allowed to stand for a length of time at this temperature. It is obvious therefore that one of the advantages of the present invention resides in the fact that the emulsion produced will remain in stable condition in summer or in winter over long periods of time. This is requisite in commercial practice since these emulsions may be held in storage or in transport for days or weeks and they should not have undergone any change during this period.

Further they will not decompose even though an antiseptic is not added to preserve the organic protective colloid, since the protective charging electrolyte, as for example the aluminum salt, prevents a-destruction of the protective colloid through fermentation or other deteriorating influences. v

a continuation in part of my applicationSerial No. 562,608 filed September 12, 1931.

The present application is similar in subject matter to co-pending application, Serial No.

, 562,608 filed September 12, 1931, for Stable emulsions and processes for their production, and is also similar in subject matter to co-pending applications Serial Nos. 638.345 filed October 18, 1932, and 745,755, filed September 27, 1934.

The present application is particularly directkilograms of gelatine, 3.2 kilograms of ferric sulg a ing said oppositely charged waterproofing matequantity of a concentrated gelatine', aluminum acetate,

ed to waterproofing and negatively charged fabric to a positively charged disperse phase which process is conveniently carried out in a single bath eliminating the need of two baths with the resultant disadvantages thereof.

The subject matter disclosed in the present application which is not specifically claimed herein is covered in said co-pen'ding or other applications.

It is to be understood that the various examples given in this application have been supplied by way of'example' and illustration and not by way of limitation and it is intended to include in the scope of the present application, all of the various modifications and changes which may be made without departing from the essence of the invention. I

1. A process. of waterproofing negatively charged textile materials which comprises subjecting them to a dilute aqueous bath containing a positively charged colloidally dispersed water insoluble fatty, waxy or oily material, a protective non-a kaline organic water soluble colloid and a soluble polyvalent metallic salt, said bath having 25 been prepared by the addition of a relatively large quantity of water to a relatively small quantity of a concentrated emuls on containing said water-insoluble material, said protective colloid and said polyvalent salt. 1

2. A process of waterproofing negatively charged textile materials, which comprises impregnating the textile with a mixture of a relatively large quantity of water and a relatively small quantity of a concentrated emulsion containing a protective non-alkaline organic water.

soluble colloid, a polyvalent water soluble metal salt and a water-insoluble fatty, waxy .or oily material, the disperse phase of said emulsion being positively charged and saidtextile absorbrial in the disperse phase from said bath by reason of its opposite electric charge.

'3. A process of waterproofing negatively charged textile materials, which comprises immersing such textiles in a bath containing a relatively'large quantity of water and a relatively small quantity of a concentrated emulsion containing glue, aluminum salt and parailin, the disperse phase of said emulsion being positively charged and said textile absorbing said oppositely charged waterproofing material in the disperse phase from said bath by reason of its opposite electric charge.

1. A process of waterproofing negatively charged textile materials, which comprises immersing them in a bath containing a relatively large quantity of water and a relatively small quantity of a concentrated emulsion containing paraifin, aluminum acetate, and glue, the dis-' perse phase of said emulsion being positively charged and said textile absorbing said oppositely charged waterproofing material in the disperse-phase from said bath by reason ofits opposite electric charge. 0

5. A process of waterproofing negatively charged textile materials, which comprises immersing them in a bath containing a relatively large quantity of water and a relatively small emulsion containing petroleum jelly and paraflin, the disperse phase of said emulsion being positively charged and said textile absorbing said oppositely charged waterproofing material 7 mersing them parts water and 1 part of a in the dis se phase from said both by reason 01 its opposite electric charge.

6. A process 0! waterproofing negatively charged textile materials which comprises imme'rsing them in a bath containing a relatively large quantity of water andarelatively small quantity of a concentrated emulsion containing gelatine',

aluminum sulphate. mineral oil and stearic acid, the disperse phase of said emulsion being post tively charged and said textile absorbing said oppositely charged waterproofing material'in' the disperse phase from said bath by reason or its opposite electric charge.

'7. A process of waterproofing negatively charged textile materials, which comprises imparts of water and 1 part of a concentrated emula mixture of slon; said emulsion consisting 0! 300 parts of paraflln, 100 parts of glue; 500 parts ot water and 140 parts of aluminum acetate, the disperse phase or said emulsion being posite electric charge. 9. A process waterproofing negatively charged textile materials, which comprises im mersing them in abeth containing 20 to 100 parts of water and 1 part of a concentratedemulsion said charged textile materials,

in a bath containing 20 to 100 absorbing said -amoxmt from to 100% o! and a water solublepolyvalent-metal salt in' an positively charged and said textile absorbing said' oppo" .sitely charged waterproofing material in the disperse phase from said bath by reason of its opv phase and then'dilutini with at least to in the bath to emulsionconsisting of a mixture of parts of gelatlne, 700 parts of water, parts or aluminum acetate, 125 parts of petroleum jelly and 125 parts '01 paraflin, the disperse phase of said emulsion being positively charged and said textile absorb- 5 ns sald opposltely charged waterproofing material in the disperse phase from said bath by reason 01' its opposite electric charge.

10. A process of waterproofing negatively which comprises immersing them in va bath containing 20 to 100 parts of water and 1 part of a concentrated emulsion. said emulsion consisting of a mixture or 1000 parts of water, 80 parts of gelatine, 50 parts or aluminum sulphate, 40 parts of mineral oil and parts or stearic acid, the disperse phase of said emulsion being positively charged and said textile absorbing said oppositely charged waterproofing material in the disperse phase from saldhath by reason or its opposite electric 11. The process 0! waterproofing textiles with diluted aqueous emulsions or water insoluble oil. waxy and fatty materials as the positively charged disperse phase, said textiles being negatiyely charged. which comprises providing a concentre-ted em v on with a positi disperse phase having asolidcontent of at lent content including .the positively e, charged lisperse phase constituting-at least 8 to so} 10% of the emulsion, a protective colloid'in the disperse phase amount ranging from 5w 100% ot'the'dispcre parts by weight oi water per part or emulsion to form the bath and immersing textile materials c l flnz'materlal in the disper e pm therefrom. a

ely charged absorb the oppositely charged 

